Process for making detergent compositions



PROCESS FOR MAKING DETERGENT COMPOSITIONS Louis E. Wells, Jr., and HenryV. Moss, Anniston, Ala, assignors to Monsanto Chemical Company, .St.Louis, Mo., a corporation of Delaware No Drawing. Application May 12,1949, Serial No. 92,954

12 Claims. (Cl. 252-135) This invention provides a detergent and aprocess for producing the same.

The object of this invention is to provide a detergent having improvedphysical properties and retentivity of its components. Another object isto provide a non-separable detergent composition comprising an activeingredient which is an oily liquid or semi-liquid material and acrystalline salt builder ingredient. A further object is to provide aprocess whereby the builder ingredient is formed in the presence of theactive ingredient.

It has been known for some time that the ethylene oxide condensationproducts of fatty acids, alcohols, amines, amides, phenols, alkylatedphenols, etc. where the ethenoxy content is greater than about 4, e. g.,from 5 to 20 moles equivalent ethylene oxide or more are oily liquids orsemi-liquids in the anhydrous state at ordinary temperature. In order toproduce a dry, free-flowing, powdery product suitable for household useit is generally the practice to mix the ethylene oxide containingcondensation products in the liquid or semi-liquid state withpulverulent crystalline salts so as to obtain a distributable powder.

According to British Patent No. 469,334, it is advantageous to employvarious calcined salts in place of the crystalline salts. Thisrecommendation is based principally upon the observation that calcinedsalts which are produced by the calcination of an alkali metal salt of amineral acid, with escape of a gaseous phase, resulted in the formationof hollow spaces within the particles. Such porous calcination productswere accordingly recommended as adsorbent materials for the liquid orsemiliquid condensation products with the object of preventing the oilycondensation products from striking through the paper package in whichthey are contained or sold.

We have now found that a more effective adsorbent material for the oilyliquid or semi-liquid ethylene oxide condensation products, is obtainedby conducting a hydration reaction in the presence of the saidcondensation products. A suitable hydration reaction may involve thehydration of an originally anhydrous or partly hydra'ted salt or it mayinvolve first a chemical reaction whereby an anhydrous or partlyhydrated salt is formed which is then followed by further hydrationwhereby a more completely hydrated salt is formed. Contrary to whatwould have been expected the hydrated salt products so produced retainthe oily liquid or semi-liquid ethylene oxide condensation products moreeffectively than those produced from calcined salts. At the same timethe present products are much more pulverulent and free flowing evenafter having been subjected to considerable pressure as during storage,and especially during storage under freezing conditions.

The tenacity with which the salts or other materials can be made toretain the oily ethylene oxide condensation products may be measured bya soaking test which is carried out by placing a pile of the product ona piece of adsorbent paper, placing a weight on the pile and thenallowing the pile to remain in this position for several days. At theend of this time the paper is removed, sol- States Patent 'ice ventextracted, the solvent removed and the residue weighed. The amount ofthe residue so recovered is a measure of the tenacity with which thesalt retains the oily condensation products.

By applying the above soaking test to a series of products produced byvarious methods it has been observed that the product produced byconducting the hydration reaction of an anhydrous salt or the morecomplete hydration of a partly hydrated salt in the presence of the oilycondensation product shows a markedly improved retentivity for the oilycondensation product. The improved product at the same time exhibits abetter color and a greater flowability than do the prior known products.

The following examples illustrate our invention:

Example 1 Anhydrous tetrasodium pyrophosphate, 100 parts by Weight, ismixed with 40 parts by weight of the oily condensation products obtainedby reacting 100 parts of tall oil with 160 parts of ethylene oxide. Themixing may be carried out manually or preferably in a mechanical mixer.To the mixture so produced, water is added gradually and with continuedmixing. The amount of water added is 'sufiicient to hydrate thetetrasodium pyrophosphate to the deca hydrate. The product so producedshows excellent retentivity of the ethylene oxide condensation productand a high rate of flow. The final product contains approximately 20% ofthe condensation product and of tetrasodium pyrophosphate deca hydrate.

Example 2 parts by weight of the oily condensation product obtained byreacting '100 parts of tall oil with 160 parts of ethylene oxide ismixed with 15 parts of water and then parts of the above solution isadded to and mixed with 203 parts of finely divided calcined anhydroustetrasodium pyrophosphate. Mixing is carried out with the aid of amechanical stirrer. After the water contained in the oily condensationproduct has reacted with the anhydrous salt a further 122 parts of waterare added to the mixture in order to hydrate the tetrasodiumpyrophosphate to the deca hydrate. The product is somewhat better inretentivity of the oily condensation product than that producedaccording to Example 1.

Example 3 Sodium acid pyrophosphate (NazHzPzO-z), 40 parts, is mixedwith 19 parts of sodium carbonate. In a separate vessel 85 parts byweight of the oily condensation .product obtained by reacting 100 partsof tall oil with parts of ethylene oxide is mixed with 15 parts of waterso as to produce an 85% solution. 23.5 parts of this aqueous solution ofoily condensation product is now added to the mixture of sodium acidpyrophosphate and sodium carbonate.

The water present in the ethylene oxide condensation product initiatesone or more of the following reactions:

and also partially hydrates the pyrophosphate salts. At this stage, themixture contains the equivalent of 54 parts of a mixture of anhydrousand mono hydrated tetrasodium pyrophosphate. Substantially 21% of thepyrophosphate has been completely hydrated. A further quantity of wateris now added to the partly hydrated mixture in order to hydrate thetetrasodium pyrop'hosphate completely or substantially so, to thedecahydrate:

NasPao'l. 10H2O In making this addition, it is assumed that all of thesodium acid pyrophosphate has been converted to tetrasodiumpyrophosphate although satisfactory results are obtainable if it isassumed that only reactions (2) and/or (3) take place and enough wateris added to completely or substantially completely yield the monohydrateor trisodium hydrogen pyrophosphate: NasHPzOrSHzO.

The further hydration of the partly hydrated tetrasodium pyrophosphatemay also be carried out by adding aqueous solutions of salts such forexample as sodium silicates. For this purpose the liquid commercial formof sodium silicates which contain from 46% to 63% of water, 9% to 18%N920 and 29% to 36% SiOz may be used.

Example 4 15 parts of the oily condensation product of tall oil andethylene oxide is added to 62 parts of finely divided anhydrous sodiumtripolyphosphate, NaaPsOio, and thoroughly mixed in a mechanical mixer.Liquid N brand silicate, 23 parts, is added and the mixing continued forapproximately 10 minutes or more. The mixed product is removed from themixer and is a cream colored powder, slightly granular and of goodretentivity. This example illustrates the hydration of sodiumtripolyphosphate by means of the water contained in the aqueoussilicate.

While the use of aqueous sodium silicates is not ordinarily looked uponwith favor by reason of the formation of sticky or gummy lumps in theproduct, we have found that when the addition of the aqueous silicate ismade to the anhydrous or partly hydrated tetrasodium pyrophosphate inthe presence of the ethylene oxide condensatlon product, the materialquickly becomes dry and free flowing.

Alkali metal salts capable of further hydration in the present reactionare for example the following sodium salts, the list herewith showingthe anhydrous salt, the intermediate hydrates, if any, and the fullyhydrated form of the salt.

Sodium carbonate:

Na2CO3, NazCOaI-IzO, Na2CO3.7H20, and

Nazcos l 0H2O Sodium sulfate:

NazSOt, N212SO4.H2O and NazSOa7I-I2O Sodium tripolyphosphate:

NasPsOio, NaPsO1o.6I-I2O. Sodium sesquicarbonate:

Na3I-I(CO3)2, NasH(CO3)2.2H2O or mixtures of normal and acid sodiumcarbonates variously known as modified sodas ranging in proportions ofconstituents from ZNaHCOgzNazCOs to NaHCOs f0 ZNazCOs.

Disodium orthophosphate:

NazHPOt, Na2HPO4.'/'H2O, NazHPOelZHzO. Trisodium orthophosphate:

By the term capable of further hydration as used in the specificationand claims, we mean either the anhydrous form of the salt or a lowerhydrate of the salt which, on reaction with water, forms a higherhydrate or the completely hydrated form of the salt. Obviously thehydrate so produced should be stable at ordinary temperatures. At leastone part by weight of a salt capable of further hydration should behydrated in the presence of from 0.1 to 1 part of the oily condensationproduct, it being understood that the relative proportion of salt tocondensation product will vary with the condensation product used.

Carboxy methyl cellulose is desirably added in amount of from 0.5% to5.0% of the final product. The product produced according to the aboveprocedure is adjusted to the following composition:

Per cent Ethylene oxide condensation product 20 Tetrasodiumpyrophosphate deca hydrate 67 Sodium silicate, NazOzSiOz ratio 1:3.2 9Carboxy methyl cellulose 1.5 Soda ash 2.5

The condensation product of tall oil and ethylene oxide may be preparedby the method described in pending application Serial No. 637,096, filedDecember 22, 1945, now abandoned, which application is assigned to thesame assignee as is the present case. According to this application,ethylene oxide in gasor liquid form is passed into ull oil at atemperature of from C. to C. until at least 0.5 part, but not less than2.3 parts of ethylene oxide has become combined per part of tall oil. Inorder to assist the condensation reaction a small amount (0.1% to 0.2%)of KOH or NaOI-l is added to the tall oil.

In place of the condensation product of tall oil with ethylene oxide, wemay employ similarly the condensation product obtained by reactingethylene oxide with one or a mixture of the following materials:

Fatty acids having at least 8 carbon atoms in the molecule and eithersaturated or unsaturated.

Alicyclic acids such as abietic acid.

Fatty alcohols having at least 8 carbon atoms in the molecule, straightor branched chain, saturated or unsaturated.

Alicyclic alcohols such as abietyl alcohol.

Fatty amines, saturated or unsaturated having at least 8 carbon atoms.

Fatty amides derived from fatty acids having at least 8 carbon atoms.

Alkylated phenols having from 6 to 10 carbon atoms in the alkyl chain.

These compounds are characterized by having an active hydrogen atomwhich is reactive with ethylene oxide to give polyglycol ether typecondensation products. The oily liquid to semi-liquid condensationproduct may contain from 5 moles to 20 or more moles of condensedethylene oxide per mole of active hydrogen containing compound.

Compounds which are reactive with sodium acid pyrophosphate and which inthe presence of water form trisodium hydrogen pyrophosphate and/ortetrasodium pyrophosphate are the alkali metal carbonates, bicarbonateor the sesquicarbonate. By reason of the availability of the sodiumsalts, I prefer to employ sodium carbonate, sodium bicarbonate or sodiumsesquicarbonate. The amount employed should be at least sufficient tocompletely convert the sodium acid pyrophosphate to trisodium hydrogenpyrophosphate, and preferably to tetra- Fodium pyrophosphate. For mostpurposes we prefer to use an excess of the sodium carbonates, since anyunreacted carbonate may advantageously remain in the final product.

Illustrative of the results obtained by the present process, we herewithgive the results of the above mentioned soaking test as applied tovarious detergent formulations produced by the prior art methods andalso by the method of the present invention.

The following formulations were prepared, in each case employing thecondensation product of tall oil with 1.6 parts of ethylene oxide perpart of tall oil.

FormulationNumber l 2 i 3 4 5 6 Condensation product. percent 20.0 2/0.0 l 12. 5 15.0 17.5 20.0 'let-rasodium pyrophosphate 40.0 40.0 40.0 40.040.0 40.0 Sodium sesquicarbonate 20.0 20.0 Starch 18.5 18. s Oarboxymethyl ceilluloseiz. 1 1. 5 1. 5 1. 5 1. 5 1. o 1. a S d' m 'licate soution H2?) 2&0 Sodium carbonate. 12. 0 12. 0 12. 0

Water added The method of formulation employed in preparing the abovewas as follows: 1 and 2 were prepared by mixing the dry ingredients, 1being a laboratory preparation and 2 being from a plant batch ofmaterial. Numbers 3 and 6 inclusive, were prepared by the method ofExample 3 of the present application. The tetrasodium pyrophosphateemployed was prepared by the calcination of hydrated disodiumorthophosphate.

Upon applying the soaking test described above, the

From the above data, it will be noted that the retentivity of the oilycondensation product has been very greatly increased by carrying out thehydration of the salts present in the presence of the condensationproduct.

What we claim is:

l. The process of increasing the retentivity of a finely dividedinorganic hydratable alkali metal detergent builder for an oilydetergent of the polyglycol ether type, which consists essentially ingradually adding an aqueous me dium to said builder while mixing thelatter in the finely divided solid state with said oily detergent in anamount varying from about 0.1 part to about 1 part of said oilydetergent for each part of said builder, said aqueous medium supplyingwater only in an amount sufficient to form a hydrate of said hydratablealkali metal detergent builder and said water incorporated with saidaqueous medium being retained in said mixture as the hydrate of saidbuilder.

2. The process of increasing the retentivity of a finely dividedinorganic hydratable alkali metal detergent builder for an oilydetergent derived from the condensation of ethylene oxide with tall oil,which consists essentially in gradually adding an aqueous medium to saiddetergent builder while mixing the latter in the finely divided solidstate with said oily detergent in an amount varying from 0.1 part toabout 1.0 part of said oily detergent for each part of said builder,said aqueous medium supplying water only in an amount sufficient to forma hydrate of said hydratable alkali metal detergent builder and saidwater incorporated with said aqueous medium being retained in saidmixture as the hydrate of said builder.

3. The process of increasing the retentivity of a finely dividedinorganic hydratable alkali metal detergent builder for an oilydetergent derived from the condensation of about 0.5 part to about 2.3parts of ethylene oxide with about 1 part of tall oil, which consistsessentially in gradually adding an aqueous medium to said detergentbuilder while mixing the latter in the finely divided solid state withsaid oily detergent in an amount varying from 0.1 part to 1 part of saidoily detergent for each part of said builder, said aqueous mediumsupplying water only in an amount suflicient to form a hydrate of saidhydratable alkali metal detergent builder and said water incorporatedwith said aqueous medium being retained in said mixture as the hydrateof said builder.

4. The process of increasing the retentivity of a finely dividedinorganic hydratable alkali metal detergent builder for an oilydetergent derived from the condensation of about 1.6 parts of ethyleneoxide with about 1 part of tall oil, which consists essentially ingradually adding an aqueous medium to said detergent builder whilemixing the latter in the finely divided solid state with said oilydetergent in an amount varying from about 0.2 to about 0.5 part of saidoily detergent for each part of said builder, said aqueous mediumsupplying water only in an amount sufiicient to form a hydrate of saidhydratable alkali metal detergent builder and said water incorporatedwith said aqueous medium being retained in said mixture as the hydrateof said builder.

5. The process defined in claim 4 wherein finely divided solidtetrasodium pyrophosphate is the hydratable alkali metal detergentbuilder employed.

6. The process defined in claim 4 wherein finely divided solid trisodiumhydrogen pyrophosphate is the hydratable alkali metal detergent builderemployed.

7. The process defined in claim 4 wherein finely divided solid sodiumtripolyphosphate is the hydratable alkali metal detergent builderemployed.

8. The process defined in claim 4 wherein the aqueous medium consists ofwater.

9. The process defined in claim 4 wherein the aqueous medium is a liquidsodium silicate containing 46% to 63% water, 9% to 18% NazO and 29% to36% SiOz.

10. The process defined in claim 4 wherein the oily detergent isemployed in an amount corresponding to about .3 part for each part ofsaid builder.

11. The process of increasing the retentivity of finely dividedanhydrous tetrasodium pyrophosphate for an oily detergent derived fromthe condensation of about 1.6 parts of ethylene oxide with about 1 partof tall oil, which consists essentially in gradually adding water tosaid salt While intimately mixing the latter in the finely divided solidstate with said oily detergent in an amount corresponding to about 0.5part of said oily detergent for each part of said tetrasodiumpyrophosphate, said Water being added only in an amount suflicient toform the decahydrate of said salt and said water being retained in saidmixture as the decahydrate of said salt.

12. The process of increasing the retentivity of finely divided sodiumtripolyphosphate for an oily detergent derived from the condensation ofethylene oxide with tall oil, which consists essentially in graduallyadding an aqueous medium to said salt while intimately mixing the latterin the finely divided solid state with said oily detergent in an amountcorresponding to about 0.2 part of said oily detergent for each part ofsaid sodium tripolyphosphate, said aqueous medium consisting of a liquidsodium silicate containing 46% to 63% water, 9% to 18% NazO and 29% to36% SiOz and being employed only in an amount sufilcient to form ahydrate of said sodium tripolyphosphate and said Water incorporated withsaid aqueous medium being retained in said mixture as the hydrate ofsaid sodium tripolyphosphate.

References Cited in the file of this patent UNITED STATES PATENTS2,154,977 Fumess Apr. 18, 1939 2,351,559 Trelfier June 13, 19442,365,215 Rhodes Dec. 19, 1944 2,427,642 Aitchison Sept. 16, 1947FOREIGN PATENTS 469,334 Great Britain July 23, 1937 490,285 GreatBritain Aug. 11, 1938

1. THE PROCESS OF INCREASING THE RETENTIVITY OF A FINELY DIVIDEDINORGANIC HYDRATABLE ALKALI METAL DETERGENT BUILDER FOR AN OILYDETERGENT OF THE POLYGLYCOL ETHER TYPE, WHICH CONSISTS ESSENTIALLY INGRADUALLY ADDING AN AQUEOUS MEDIUM TO SAID BUILDER WHILE MIXING THELATTER IN THE FINELY DIVIDED SOLID STATE WITH SAID OILY DETERGENT IN ANAMOUNT VARYING FROM ABOUT 0.1 PART TO ABOUT 1 PART OF SAID OILYDETERGENT FOR EACH PART OF SAID BUILDER, SAID AQUEOUS MEDIUM SUPPLYINGWATER ONLY IN AN AMOUNT SUFFICIENT TO FORM A HYDRATE OF SAID HYDRATABLEALKALI METAL DETERGENT BUILDER AND SAID WATER INCORPORATED WITH SAIDAQUEOUS MEDIUM BEING RETAINED IN SAID MIXTURE AS THE HYDRATE OF SAIDBUILDER.